DE60024894T2 - Intumescent polymer composition - Google Patents

Abstract

An intumescent polymer composition includes a matrix polymer, an acid catalyst source, a nitrogen source and an ionic phyllosilicate synergist having substantial cationic exchange capacity. Particularly preferred ionic phyllosilicates are montmorillonoids whereas pentaerythritol phosphate is a preferred acid catalyst source:

Description

technical area

The The present invention relates generally to intumescent, flame retardant polymers, and more particularly, intumescent compositions comprising a matrix polymer, an effervescent composition, an acidic catalyst component, a nitrogen source and an ionic phyllosilicate synergist.

background

effervescent, Flame retardant polymer compositions are well known in the art. by virtue of possible ecological and toxicity problems there is an increasing interest in antimony and halogen-free systems, which impart the desired flame retardant properties to a polymeric article. Phosphorus based compositions are for example in the publications No. WO 99/43747 and WO 97/41173.

The 747 publication entitled Flame Retardant Polymer Blends discloses an antimony-free combination a flame retardant based on phosphate, in particular an aryl diphosphate, and an organic clay that is listed that they are polymer blends, in particular polyphenylene ether-polystyrene blends and blends of polycarbonates with styrene copolymers such as ABS copolymers confer synergistic flame retardant properties. The polyphenylene ether-polystyrene blends that are free of fluorocarbon additives are preferred according to the disclosure.

The 173 publication entitled Flame Retardant Composition for Polymers a flame retardant composition adapted to that it is mixed with a polymer substrate, whereby the substrate Flame retardancy, the composition comprising: (a) a bicyclic flame retardant phosphorus compound such as, which contains one or more pentaerythritol phosphate alcohol residues by bis (pentaerythritol) phosphate alcohol carbonate; (b) an intumescent, Flame-retardant compound containing nitrogen and phosphorus, such as Melamine phosphate, and (c) a monophosphate ester compound for enhancing the Charring and processing characteristics of the composition in the polymer substrate, like a liquid, aryl group-containing phosphate ester compound. The monophosphate ester compound is typically triphenyl phosphate.

Please refer See also U.S. Patent No. 4,454,064, Halpern et al., which discloses a method for the preparation of pentaerythritol phosphate by mixing Pentaerythritol and phosphorus oxychloride in a solvent and heating to a temperature of 75 to 125 ° C as well as the U.S. patent No. 5,237,085, Telschaw et al., Which describe the synthesis of phosphorus heterocycles based on pentaerythritol by the reaction of a pentaerythritol polyol using either a trivalent or a pentavalent compound an aryl phosphate solvent at elevated Temperature teaches. A variety of bicyclic phosphate compounds is also disclosed in U.S. Patent No. 3,293,327, Hechenbleikner et al.

in the U.S. Patent No. 4,341,694, Halpern, is reported to be intumescent flame retardant Compositions containing 2,6,7-trioxa-1-phosphobicyclo [2.2.2] octane-4-methanol-1-oxide and one from the group melamine, ammeline, benzoguanidine, guanidine, Urea and salts thereof include selected nitrogen compound, intumescent and be easily adapted to a variety of including various resins Polyolefins, polyvinylaromatic resins, polycarbonates, polyacrylates, Give polyamides, PVC and blends thereof flame retardancy.

The U.S. Patent No. 5,204,393, Nalepa et al., Describes a flame retardant, foaming Polyolefin containing a combination of ammonium polyphosphate, tris (2-hydroxyethyl) isocyanurate, Melamine cyanurate and a selected one Silica in an amount of 0.5% up to an amount that equal to half the amount by weight of tris (2-hydroxyethyl) isocyanurate is included.

It is generally believed that the intumescent polymer systems may be formed by (1) a carbonizing or char-forming component, which may be the polymer itself, (2) an acid-forming component serving as a catalyst, and (3) a propellant or catalyst Blowing agents, typically a nitrogen source for both ammonia and N ₂ , function. The larger the volume of carbonized material, the better the insulation, while the inner core of the cross section should be cellular and closed cell. In addition, the surface crust should be thick, continuous and impermeable be. See DJ Sharp, Intumescent Fire Retardants for Plastics - A Continuance. The catalyst or acid generating component is often a phosphorus derivative whose function is to catalyze dehydration. See M. Lewin, Some Aspects of Synergism and Catalysis in FR of Polymeric Materials - An Overview, Ninth Annual BCC Conference on Flame Retardancy, Business Communications Co., Inc., Norwalk Connecticut, which describes ammonium polyphosphate as the acid generating component and nitrogen source in a polypropylene system in which the polymer itself is the carbonizing or charred material forming agent.

Maybe even more typical is an organic polyol as a carbonizing agent and melamine or a melamine derivative used as blowing agent. Please refer D. Scharf et al., Studies on Flame Retardant Intumescent Char: Part 1, Fire Safety Journal 19, pp. 103-117, Elsevier (Ireland, 1992). In this publication It is reported that titanium dioxide in suitable amounts is a reinforcing or exerts synergistic flame retardant effect, while tin (II) oxide is antagonistic is. equally It has been reported that zinc and manganese salts affect APP behavior favor can. See Lewin et al., Mn and Zn Compounds as Catalysts of Intumescent Flame Retardancy of Polypropylene, May, 2000, BCC Confercence.

In every polymer system is desirable from the cost perspective, to limit or minimize expensive additives. Furthermore can Additive detrimental effects on the processing or properties have, of course, what all the more pronounced the more the additive loading of the system increases. The commercial one Success of frothing Polymer systems is characterized by the high loading with an acid-generating Component and a propellant that are required in terms of the flame resistance the desired Classification (typically 94V-0), clearly limited.

Summary the invention

According to the present Invention, it has been found that certain ionic phyllosilicates, especially silicates with montmorillonoid layers, a synergistic Effect on intumescent Exercise polymer compositions, which makes it possible is, the amount of additives that for a given degree of flame resistance are required to degrade, causing, for example, under UL-94 standards will maintain a rating as V-0 and otherwise known acid and nitrogen sources are used. Thus, according to a The first aspect of the present invention is an intumescent polymer composition available comprising: a matrix polymer composition, an acid catalyst source, a nitrogen source and an ionic phyllosilicate in an amount from about 0.1 to about 2% by weight of the composition, wherein the ionic Phyllosilicate has a cation exchange capacity of at least about 5 milliequivalents per 100 g of it and capable of doing so is, the frothing to promote the composition in a synergistic way.

In a particularly preferred class of compositions is a foaming Polypropylene composition, comprising: polypropylene, a source for a catalyst for a cyclic organophosphoric acid, a nitrogen source selected from amines, ureas, guanidines, guanamines, s-triazines, Amino acids, Including salts Phosphate, phosphonate, phosphinate, borate, cyanurate and sulfate salts and mixtures of the preceding group and an ionic one Montmorillonoid phyllosilicate, wherein the ionic phyllosilicate in an amount of about 0.1 to about 2% by weight.

In Another aspect of the present invention is a flame retardant An additive composition for dispersing in a matrix polymer composition to promote a frothing available made, comprising: an acid catalyst source, a nitrogen source, an ionic phyllosilicate having an ion exchange capacity of at least about 5 milliequivalents per 100 g thereof and optionally an organic polyol as carbonating, verkohlungsförderndes Agent, wherein the ionic phyllosilicate in an amount of about 0.5 to about 10% by weight of the composition is present.

Full description

The invention will be described in detail below with reference to numerous exemplary, illustrative and preferred embodiments thereof for purposes of description only. Modification of such embodiments within the scope of the invention recited in the appended claims will be readily apparent to those skilled in the art. Furthermore, it can be seen that the components of the invention undergo a chemical interaction to form other materials, especially during combustion. Therefore, the invention relates to the compositions of the invention independently whether a chemical interaction has taken place or not; that is, the invention includes both the listed compositions and their reaction products.

The Compositions of the invention typically comprise a matrix polymer, a carbonizing and foaming or a nitrogen source component. These components can be used in the same chemical compound. For example, ammonium polyphosphate is used both as an acid source as well as a nitrogen source, as will be readily apparent to one skilled in the art is. equally pentaerythritol phosphate alcohol (PEPA) serves both as an acid source as well as a carbonating agent. Melamine phosphate can be carbon for the charred material, nitrogen for foaming and acid for catalysing dehydration generate and is thus a particularly preferred ingredient.

In some embodiments become the acid source and the nitrogen source completely or partially added as a single chemical compound, those from the ammonium phosphate, ammonium polyphosphate, ammonium pyrophosphate and mixtures thereof is selected.

Foaming polymer compositions are the ones that foam and char and thereby produce a flame resistance, whereby the volume typically more than 50%, preferably in the Magnitude of 100%, based on the unreacted volume of the composition. The compositions thus typically comprise an acid catalyst source, a nitrogen source and a carbonating agent in which it may be the polymer matrix itself or a polyol, or you can by means of a multifunctional ingredient such as pentaerythritol phosphate alcohol to be provided. The ionic phyllosilicates work to the effect that it is the amount of additive, be it an acid or an acid a nitrogen source, thereby providing the composition with a Classification as 94V-0 is awarded. Typically works this ionic phyllosilicate to the extent that it requires the amount Acid-, the required nitrogen and the required carbonization additive by at least about 10% and preferably at least 20% on the additive weight, reduced.

Acid sources can be borates, sulfates, sulfites, nitrates, phosphates, phosphonates, melamine or other salts of the foregoing and so on. Exemplary materials include alkyl diphenyl phosphates, trimethyl phosphate (C ₃ H ₉ O ₄ P), triphenyl phosphine oxide (C ₁₈ H ₁₅ OP), triphenyl phosphate (C ₁₈ H ₁₅ O ₄ P), ammonium phosphates such as monoammonium phosphate (NH ₄ H ₂ PO ₄ ) and diammonium phosphate, (NH ₄ ) ₂ HPO ₄ , ammonium polyphosphate (NH ₄ PO ₃ ) _n , amine phosphates such as melamine phosphate, eg melamine orthophosphate (C ₃ H ₆ N ₆ H ₃ O ₄ P), dimelamine orthophosphate (2 C ₃ H ₆ N ₆ H ₃ O ₄ P), melamine pyrophosphate (2 C ₉ H ₆ N ₆ H ₄ O ₂ P ₂ ) and the like, trialkyl phosphates such as triethyl phosphate (C ₆ H ₁₅ O ₄ P) or trioctyl phosphate (C ₂₄ H ₅₁ O ₄ P), dimethyl methylphosphonate (C ₃ H ₉ O ₃ P) and diethyl ethyl phosphonate (C ₆ H ₁₅ O ₃ P), halogenated alkyl phosphates and phosphonates such as tris (2-chloroethyl) phosphate (C ₆ H ₁₂ Cl ₃ O ₄ P), tris (1-chloro-2-one) propyl) phosphate (C ₉ H ₁₈ Cl ₃ O ₄ P), tris (1,3-dichloro-2-propyl) phosphate (C ₉ H ₁₅ Cl ₆ O ₄ P), tris [3-bromo-2,2- bis (bromomethyl) propyl] phosphate (C ₁₅ H ₂₄ Br ₉ O ₄ P) and bis (2-chloroethyl) -2-chloro rethylphosphonat, diphosphates such as 2-Chlorethyldiphosphate such as tetrakis (2-chloroethyl) Ethylenoxyethylendiphosphat (C ₁₂ H ₂₄ Cl ₄ O ₉ P _2), C ₁₃ H ₂₄ Cl ₆ O ₈ P ₂ (Antiblaze 100 from Albright & Wilson), 2 Chloroethyl 2-bromoethyl-3-bromobenzene phosphate (C ₉ H ₁₈ Br ₂ ClO ₄ P) from Great Lakes Chemical Corporation - Firemaster 836, cyclic phosphonates such as C ₁₅ H ₃₁ O ₉ P ₃ (Antiblaze 19 and 1045 from Albright & Wilson), cyclic neopentyl thiophosphoric anhydride, aryl phosphates such as cresyl diphenyl phosphate (C ₁₉ H ₁₇ O ₄ P), triaryl phosphates such as triphenyl phosphate (C ₁₈ H ₁₅ O ₄ P), tetraphenyl resorcinol diphosphate (C ₃₈ H ₂₄ O ₈ P), tris (2,4-dibromophenyl ) phosphate (C ₁₈ H ₉ Br ₆ O ₄ P), diphosphine oxides such as Cyagard RF1204 from American Cyanamid.

bicyclic Organophosphorus compounds used in the present invention as Säurekatalystorquelle are useful are pentaerythritol phosphite, trimethylol propane phosphite, Trimethylolethane phosphite, trimethylolbutane phosphite, trimethylolisobutene phosphite, Trimethylolpentanphosphit, Tri methylolhexanphosphit, Trimethylolheptanphosphit, Trimethylolctane phosphite, trimethylolnonane phosphite, trimethylolundecane phosphite, Trimethylolheptadecane phosphite, pentaerythritol phosphate, pentaerythritol thiophosphate, Pentaerythritolelenophosphate, trimethylolpropane phosphate, trimethylolpropane thiophosphate, Trimethylolpropane selenophosphate, trimethylolethane phosphate, trimethylolethanthiophosphate, Trimethylolethane selenophosphate, trimethylolbutane phosphate, trimethylolbutane thiophosphate, Trimethylol pentane phosphate, trimethylol pentane thiophosphate, trimethylol pentane selenophosphate, Trimethylolhexane phosphate, trimethylolhexanthiophosphate, trimethylolheptane phosphate, Trimethylol heptane thiophosphate, trimethylol octane phosphate, trimethylol octanthiophosphate, Trimethylolnonane phosphate, trimethylolnonanthiophosphate, trimethylolnonanselenophosphate, Trimethylol decane phosphate, trimethylol decane thiophosphate, trimethylolundecane phosphate, Trimethylolundecanthiophosphat, Trimethylolheptadecanphosphat, Trimethylolheptadecanthiophosphat and trimethylolheptadenocyclose phosphate.

Particularly preferred is pentaerythritol phosphate alcohol, sometimes simply pentaerythritol phat and has the following general structure:

derivatives The bicyclic phosphorus compounds can also be used. For example, esters, ethers and carbonates of pentaerythritol phosphate alcohol known flame retardant components of intumescent systems.

additional examples for Phosphorus-containing flame retardants include melamine salts of organophosphates such as melamine phenyl phosphate and melamine amyl phosphate.

According to the present Invention is a combination of an ionic phyllosilicate, an acid catalyst source, a nitrogen source and optionally a charring promoter Species processed into a resin, whereby a resin composition or a resin product is obtained, the improved flame retardant Has properties and / or lower overall costs. If that flame-retardant agent has a sufficient foaming behavior, can the flame retardant material with the ionic phyllosilicate without the use of a separate charring Compound used, creating an additive system for flame retardant applications obtained in resins. Char additive can, however, if desired are useful and include polyhydric alcohols such as pentaerythritol, Dipentaerythritol, tripentaerythritol, inositol, adonite, dulcitol and 1,3,5-tris (2-hydroxyethyl) cyanuric acid as well Pentate salts of amino-s-triazines as described in Fleenor, Jr., U.S. Patent No. 4,253,972, which is incorporated herein by reference is taken is disclosed. Examples of polymeric carbonization Additives include novolac resins, polyphenylene oxides and polycarbonates. When charring Additives are included in the phosphorus-containing flame retardant additive should be present in an amount of from about 1% to about 10% by weight, based on the weight of the flame retardant to be provided Polymer, to be added.

Compounds useful as nitrogen sources include any suitable compounds which produce N ₂ and optionally ammonia, such as amines, ureas, guanidines, guanamines, s-triazines, amino acids and their salts including phosphate, phosphonate, phosphinate, borate , Cyanurate and sulfate salts. Some specific examples are melamine, urea, benzoguanamine, ammeline, guanidine, cyanoguanidine and glycine; Melamine phosphate, melamine pyrophosphate and melamine polyphosphate; Ammonium phosphate, ammonium pyrophosphate and ammonium polyphosphate, ethylenediamine phosphate, melamine or ammonium cyanurate and melamine or ammonium borate. Most preferred are melamine phosphate and ammonium polyphosphate.

The features and classification of layered silicates are described in detail in An Introduction to Clay Colloid Chemistry, H. Van Olphen, eds., Chap. 5, pp. 57-77, which is incorporated herein by reference. In general, clays are phyllosilicates having two-dimensional arrays of silicon-oxygen tetrahedra and two-dimensional arrays of aluminum or magnesium-oxygen-hydroxyl octahedra. Of particular interest in the present invention are the ionic-characterized phyllosilicates, ie, those in which the silicates are characterized by a substantial cation exchange capacity of at least about 5 milliequivalents (meq) per 100 grams of clay and here - as opposed to substantially neutral sheet silicates such as talc or kaolinite having a cation exchange capacity of less than about 5 milliequivalents per 100 grams of material - ionic phyllosilicates or layered silicates. Particularly preferred are those layered silicates in which the cation exchange capacity of the layered silicate is greater than about 25 meq of cation exchange capacity per 100 g of silicate. Most preferred are those smectite-class phyllosilicates, also referred to in the art as montmorillonoid clays, which typically have cation exchange capacities of about 70 meq or greater than 100 grams of material. Clays useful in accordance with the present invention can have cation exchange capacities of up to about 150 meq per 100 g of material. Montmorillonoid silicates are further characterized by undergoing reversible expansion upon absorption of water and having a characteristic structure in which water molecules are sandwiched between sheets consisting of two layers of silicon atoms including a nominal layer of aluminum and / or magnesium wherein the silicon and the aluminum / magnesium are variously exemplified by other elements described hereinafter replaced. Iron ionic layered phyllosilicates are believed to be particularly preferred because iron has an antagonistic effect on the foaming behavior of the system. Preferred ionic phyllosilicates are those having less than about 3 weight percent iron, with less than about 1 weight percent being most preferred.

Especially preferred montmorillonoids for use in conjunction with The invention includes sodium montmorillonite clay and sodium hectorite clay (Aluminum and / or magnesium-containing silicates), as further here is discussed.

With inorganic cations (for example of an alkali metal) or organic substances reacted (organophilic) smectite clays, such as Montmorillonite clay or any other clay with an aspect ratio of at least 40, preferably at least 50, more preferably at least 75, are ordinary those used in connection with the present invention become. examples for suitable clays include phyllosilicates such as smectite clay materials, e.g. Montmorillonite, in particular sodium montmorillonite; magnesium montmorillonite and / or calcium montmorillonite; nontronite; beidellite; volkonskoite; hectorite; laponite; saponite; sauconite; Vermiculite. Other useful ones Layered materials are illites like micaceous materials and mixed illite / smectite layer minerals, optionally through a reaction or ion exchange are made organophilic.

Formel II

wobei X = P oder N ist und wobei Y = S oder O ist und
wobei R₁, R₂, R₃ und R₄, die gleich oder verschieden sind, H oder organische Reste wie lineare oder verzweigte Alkyl-, Aryl- oder Aralkylreste mit 1 bis 24 Kohlenstoffatomen sind.Suitable organic cations entrapped by ion exchange in the spaces between the layers between adjacent platelets of layered materials may be primary, secondary, tertiary or quaternary onium ions of formula I or formula II as follows:

Formula II

where X = P or N and where Y = S or O and
wherein R ₁ , R ₂ , R ₃ and R ₄ , which are the same or different, are H or organic radicals, such as linear or branched alkyl, aryl or aralkyl radicals having 1 to 24 carbon atoms.

The more preferred onium ions are quaternary ammonium ions of the formula I wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and are selected from the group consisting of H, an alkyl, benzyl, a substituted benzyl substituted or halo substituted by, for example, an alkyl with a straight or branched chain, an ethoxylated or propoxylated alkyl; an ethoxylated or propoxylated benzyl, eg 1-10 moles of an ethoxylation or 1-10 moles of a propoxylation.

Among the preferred silicate layer materials are phyllosilicates of the 2: 1 type having a negative charge on the layers, ranging from 0.018 to 0.36 charges per formula unit and up to 0.55 charges per formula unit, and a corresponding number of exchangeable metal cations in the spaces between the layers. As stated above, the most preferred layer materials are smectite (montmorillonoid) type clay materials such as montmorillonite, nontronite, beidellite, volkonskoite, hectorite and saponite. The preferred clay materials usually include interlayer cations such as Na ⁺ , Ca ^{+ 2} , K ⁺ , Mg ^{+ 2} , NH ₄ ^+, and the like, including mixtures thereof.

The Amount of organic cationic compound used when needed can be, such as an onium ion or a protonated amine, with reacted with the layered silicate materials or with these an ion exchange may be substantially between 2%, preferably at least about 10%, and about 200%, by dry weight of the layered silicate material.

The Composition may further include metal oxides or metal salts which further improve the flame-retardant effectiveness. Suitable metals include, for example, aluminum, titanium, chromium, manganese, iron, Cobalt, nickel, copper, zinc, zirconium and tin. Oxides or salts including zinc or manganese organic and inorganic salts are preferred, with zinc borate most preferred.

The Matrix or host polymers prepared according to the present invention used include thermoplastics and thermosets. thermosets include suitable polyesters, polyurethanes and epoxies. thermoplastic Matrix polymers include vinyl polymers such as styrene, styrene copolymers and polyolefins as well as thermoplastic polyesters and polyurethanes. Polyolefins are made from the polymerization of one or more monomers prepared from ethene, propene, isobutylene, 1-butene, 4-methyl-1-pentene or α-olefins having 5-18 carbon atoms existing group selected are. The polymers can also contain minor amounts of units resulting from a copolymerization with monomers such as vinyl acetate and alkyl (meth) acrylate esters such as butyl acrylate come.

The Matrix polymer composition may contain fillers, impact modifiers, Processing aids and the like, such as hereinafter described.

Optionally, a large number of siliceous materials may be used as fillers in addition to the other components of the intumescent compositions without altering the basic and intumescent nature of the composition imparted by the ingredients listed above. Suitable fillers may include diatomite, perlite, pumice, pyrophyllite, silica and talc. These minerals may consist of an alkali metal oxide or alkaline earth element oxide and silica together with a minor amount of water and other elements. Talc includes, for example, about 25% to 35% MgO, 35-60% SiO _2, and about 5% H ₂ O.

Other fillers such as calcium carbonate and reinforcing agents, Toughening agents, pigments and the like may also be used as further discussed below.

Fiber-shaped reinforcing agent are common Needle crystals, glass, mineral wool, calcium sulfate, potassium titanate, Boron, alumina, sodium aluminum, hydroxycarbonate and so on.

Appropriately extruded polymeric compositions can coloring agents for the aesthetic Incentive, preferably titanium dioxide, carbon black and other opacifiers lock in. The compositions can minor amounts of other additives such as lubricants and antioxidants include. These articles of manufacture can be used in a suitable manner Colored pigments or dyes be. Pigments are considered small insoluble organic or inorganic Defines particles dispersed in the resin medium for opacity or translucence to promote. Useful pigments include carbon black, Titanium dioxide, zinc oxide, iron oxides and mixed metal oxides. dyes are soluble and soluble in the plastic and can used alone or in combination with pigments to colors based on pigments lightening. All such coloring Means can can be used in a variety of modes that have a dry color, conventional Color concentrates, a liquid color and a pre-colored Include resin.

The The polymeric composition of this invention may further include one or contain several agents to improve the impact resistance. So-called core-shell polymers consisting of a rubbery core, on which one or more bowls were grafted can be used become. The core usually exists essentially of an acrylate rubber or a butadiene rubber. One or more bowls can grafted to the core. Usually these shells exist Mostly from a vinyl aromatic compound and / or a vinyl cyanide and / or an alkyl (meth) acrylate and / or (meth) acrylic acid. Of the Core and / or shell (s) often comprise multifunctional compounds, which can serve as crosslinking agents and / or grafting agents. These Polymers become ordinary made in several stages.

Olefin-containing copolymers such as olefin acrylates and olefinic terpolymer can also be used as impact modifiers in the present compositions. An example of an olefin-acrylate copolymer impact modifier is the ethylene-ethyl acrylate copolymer known as DPD-6169 from Union Carbide is fair. Other higher olefin monomers, for example, propylene and n-butyl acrylate, can be used as copolymers with alkyl acrylates. The olefin-diene terpolymers are well known in the art and usually fall within the EPDM (ethylene-propylene-diene) terpolymer family. They are commercially available, for example, as EPSYN 704 from Copolymer Rubber Company. They are more fully described in U.S. Patent No. 4,559,388, which is expressly incorporated herein by reference.

Various Rubber polymers and copolymers may also be used as impact modifiers be used. examples for such rubbery polymers are polybutadiene, polyisoprene and various other polymers or copolymers having a rubbery Diene monomer.

styrene-containing Polymers can also be used as impact modifier. Examples of such Polymers are acrylonitrile-butadiene-styrene, styrene-acrylonitrile, acrylonitrile-butadiene-α-methylstyrene, Styrene-butadiene, styrene-butadiene-styrene, Diethylene-butadiene-styrene, methacrylate-butadiene-styrene, ABS with grafted rubber of high rubber content and other styrene-containing rubbers High impact polymers such as polystyrene with high impact resistance. Other known impact modifiers include various elastomeric materials such as organic silicone rubbers, elastomeric fluorohydrocarbons, elastomeric polyesters, statistical Block polysiloxane-polycarbonate copolymers and the like. In some embodiments For example, the preferred organopolysiloxane-polycarbonate block copolymers are the dimethylsiloxane-polycarbonate block copolymers.

The The present invention particularly relates to flame retardant compositions, which are classified for example by the standard UL-94.

Of the UL-94 standard for Flammability testing of plastic materials for parts in devices and devices includes several subtests, the most interesting ones being tests but are small and classify materials as 94V-0, 94V-1 or 94V-2. This is a small scale vertical burning test, in which a rod of the material to be tested Over for 10 s a small flame is hung vertically. The flame is removed, and the duration of a burn is measured. Once the afterburning stopped has, becomes the ignition source for one 10 seconds Period of exposure, removed, and the afterburning or afterglow period is being measured. The test is performed on 5 specimens to accumulated and individual results. Each bar is 125 mm long × 13 mm wide × minimum and maximum thickness, which depends on the end use. Typical thicknesses are 1/8 inch, 1/16 inch and 1/32 inch, whereby it is usually difficult to use thinner rods highest Classification to receive.

criteria to comply with the different classifications are in the following Table listed.

Table 1 - Flammability Ratings

In the following examples, various compositions were replaced by a melt formulation tion of the various components listed below, using an extruder with a bulb temperature of about 400 ° F, followed by injection molding into UL test plates in a mold at a temperature of about 120 ° F. The panels were then rated for flammability as indicated above.

Examples 1 to 18

The demonstrate the following examples, such as the flame retardant property a mixture of pentaerythritol phosphate alcohol (PEPA) and melamine phosphate with a weight ratio of 2: 3 in polypropylene with montmorillonite clay materials improved can be. To obtain a rating of 94V-0 for the polypropylene Himont 6524 (MFI = 6) is at least 21% of the PEPA: melamine phosphate mixture required. A formulation of 20% of the PEPA: melamine phosphate mixture and 1% Cloisit 15A (Organoclay, Southern Clay Products) also has a rating of 94V-0. This indicates that the flame retardant Component be replaced by low concentrations of a clay can sacrifice without the UL-94 rating. At a 0.8% load with cloisite 15A, only 19% of the PEPA: melamine phosphate mixture required to obtain a 94V-0 rating while formulations, who only had a slightly lower or higher clay content, none Classification of 94V-0 (Table 2). This demonstrates the Need to use the sound additive in a well-defined Range of loading concentrations.

The Use of an experimental brand organoclone also yields System with flame retardant properties similar to those described above System similar are. In this case, the stress concentration of the PEPA: melamine phosphate mixture with a weight ratio even further reduced by 2: 3, without the help of the Test method UL-94 given flammability property (Table 3).

Table 4 demonstrates that sodium montmorillonite in the polypropylene system gives improved flame retardancy while talc, glass, TiO ₂ and kaolin do not interact synergistically with the catalyst and nitrogen sources.

Examples 19-28

• (Alle Metalle sind als im Mineral komplexierte Oxide ausgedrückt.)

Tabelle 6 – Hectoritton C Allgemeine Beschreibung: Mikronisierter Natriumhectoritton hoher Reinheit, bestehend aus mikrofeinen Teilchen. Helligkeit (G.E.): Mindestens 70 Viskosität: 2500–5500 bei einem Feststoffgehalt von 5 % pH-Wert 2 %ige Dispersion: 9,0–11,0 Größe der nassen Teilchen: Mindestens 99,00 % feiner als 325 mesh (44 μm). Elementaranalyse: Trioktaedrischer Smectit, eine dreischichtige, expandierende Mineralstruktur: M⁺ ₃₃ (Mg_2,67Li₃₃)Si₄O₁₀(OH,F)₂·n H₂O M = Austauschbare Kationen: Na, Ca und Mg. Aufgeführte typische Werte sind nicht als starre Spezifikation aufzufassen.

• (Alle Metalle sind als im Mineral komplexierte Oxide ausgedrückt.)

In the following examples, additive compositions were prepared from 48.5% pentaerythritol phthalic alcohol, 48.5% melamine phosphate and 3% either sodium montmorillonite clay A, B or hectoritone C mixed with polypropylene as listed above and made into 1/16-inch test bars. Sodium montmorillonite clay A is available from Southern Clay, Inc., grade Cloisit Na. The sodium montmorillonite clay B had the characteristics listed in Table 5 while hectorite C was characterized in Table 6. Table 5 - Sodium montmorillonite clay B General description: Specially processed, water-washed sodium montmorillonite clay. Brightness (GE): 83-87 Viscosity: 250-500 cp (at a solids content of 5%) PH value 2% dispersion: 8.5-10.5 Size of wet particles: at least 99.00% finer than 325 mesh (44 μm) Elemental analysis: Listed typical values are not to be construed as a rigid specification.

• (All metals are expressed as oxides complexed in the mineral.)

Table 6 - Hectorite C General description: Micronised sodium hectorite clay of high purity consisting of microfine particles. Brightness (GE): At least 70 Viscosity: 2500-5500 at a solids content of 5% PH value 2% dispersion: 9.0-11.0 Size of wet particles: At least 99.00% finer than 325 mesh (44 μm). Elemental analysis: Trioctahedral smectite, a three-layer, expanding mineral structure: M ⁺ ₃₃ (Mg _2.67 Li ₃₃ ) Si ₄ O ₁₀ (OH, F) ₂ · n H ₂ OM = Interchangeable cations: Na, Ca and Mg. Typical values reported are not as a rigid specification.

• (All metals are expressed as oxides complexed in the mineral.)

Table 7 - Compositions of PP / sodium montmorillonite A (SMA) / pentaerythritol phosphate alcohol (PEPA) / melamine phosphate (MEP); FR = 3% SMA; 48.5% PEPA; 48.5% MEP

• ¹ Four bars of ten do not crack (> 450% stretch)

Table 8 - Compositions of PP / sodium montmorillonite B (SMB) / pentaerythritol phosphate alcohol (PEPA) / melamine phosphate (MEP); FR = 3% SMB; 48.5% PEPA; 48.5% MEP

Table 9 - Compositions of PP / hectorite C (HC) / pentaerythritol phosphate alcohol (PEPA) / melamine phosphate (MEP); FR - 3% HC; 48.5% PEPA; 48.5% MEP

Examples 29 to 35

The The following examples illustrate the effectiveness of various (APP) FR / Polypropylene compositions based on ammonium polyphosphate, which were made and tested as above. In the used particulate ammonium polyphosphate composition a commercially available one Product that is believed to be mainly around APP is, but also contains other additives.

Table 10 - Ammonium polyphosphate (APP) FR / polypropylene compositions

Examples 36 to 41

The The following examples in Table 11 demonstrate the effect of Zinc borate on a flame-retardant polymer composition consisting of the stated amounts of polypropylene, the flame retardant FRD, which is 3% sodium montmorillonite clay B, 48.5% pentaerythritol phosphate alcohol and 48.5% melamine phosphate. The different Compositions were prepared and rated as listed above.

Table 11 Compositions of zinc borate / FRD / PP

As from the above is the ionic montmorillonoid phyllosilicate typically in amounts of from about 0.3 to 1.5% by weight, based on the weight of the composition, included, of about 0.5 to 0.7 are sometimes particularly preferred. The sources of the acidic Catalyst and the nitrogen are in compositions by a classification of 94V-0 are marked, typically in Amounts of less than about 25% by weight of the composition, and preferably less than 18 wt .-% present.

The weight ratio the source for the acid catalyst to the nitrogen source is in some embodiments about 70:30 to about 30:70 or others from about 60:40 to 40:60. In some embodiments are weight ratios the source for the acid catalyst to the nitrogen source from about 45:55 to about 55:45 particularly preferred.

Within the scope of the present invention are additive compositions for dispersion in a matrix polymer composition which according to the above description contain an acid source, a nitrogen source, an ionic phyllosilicate, optionally a carbonizing or charring promoter and / or optionally a metal oxide or metal salt synergist, as in the above Examples emerge. In such compositions, the ionic phyllosilicate is typically present in an amount of from about 0.5 to about 10 percent by weight, and the content of the acid and nitrogen sources correspond to equal ranges in the polymer matrix when blended with the matrix polymer composition in a ratio of about 1 part of the additive composition to about 4-5 parts of the matrix polymer composition Zung.

Even though the invention in connection with numerous embodiments have been described are modifications of the above illustrated embodiments within the scope of the present invention for those skilled in the art seen.

• (1) Eine aufschäumende Polymer-Zusammensetzung, umfassend (a) eine Matrix-Polymer-Zusammensetzung, (b) eine Säurekatalysatorquelle, (c) eine Stickstoff-Quelle und (d) ein ionisches Phyllosilicat in einer Menge von etwa 0,1 bis etwa 2 Gew.-% der Zusammensetzung, wobei das ionische Phyllosilicat eine Kationenaustausch-Kapazität von wenigstens 5 Milliäquivalenten pro 100 g desselben hat und das ionische Phyllosilicat das Verschäumen der Zusammensetzung auf synergistische Weise fördern kann,
• (2) Aufschäumende Zusammensetzung gemäß (1), wobei das ionische Phyllosilicat ein ionisches Montmorillonoid-Phyllosilicat ist.
• (3) Aufschäumende Zusammensetzung gemäß (2), wobei das Montmorillonoid-Mineral einen Ton umfasst, der aus der Gruppe ausgewählt ist, bestehend aus Montmorillonit und Hektorit.
• (4) Aufschäumende Zusammensetzung gemäß (2), wobei das ionische Montmorillonoid-Phyllosilicat ein organisches Montmorillonoid-Mineral ist.
• (5) Aufschäumende Zusammensetzung gemäß (2), wobei das Montmorillonoid-Mineral ein Natrium-Montmorillonit ist.
• (6) Aufschäumende Zusammensetzung gemäß (2), wobei die Säurekatalysatorquelle eine Organophosphor-Verbindung ist.
• (7) Aufschäumende Zusammensetzung gemäß (2), wobei die Stickstoff-Quelle Melamin oder ein Salz desselben ist.
• (8) Aufschäumende Zusammensetzung gemäß (2), wobei das Matrix-Polymer ein Polyolefin ist und das ionische Montmorillonoid-Phyllosilicat in einer Menge von etwa 0,3 bis etwa 1,5 Gew.-% der Zusammensetzung vorliegt.
• (9) Aufschäumende Zusammensetzung gemäß (8), wobei das ionische Montmorillonoid-Phyllosilicat in einer Menge von etwa 0,5 bis etwa 0,7 Gew.-% der Zusammensetzung vorliegt.
• (10) Aufschäumende Zusammensetzung gemäß (8), wobei die Matrix-Polymer-Zusammensetzung im Wesentlichen aus Polypropylen besteht.
• (11) Aufschäumende Zusammensetzung gemäß (1), wobei die Zusammensetzung weiterhin ein Metalloxid oder Metallsalz umfasst.
• (12) Aufschäumende Zusammensetzung gemäß (11), wobei die Zusammensetzung ein Metallsalz umfasst und das Salz Zinkborat ist.
• (13) Aufschäumende Zusammensetzung gemäß (2), wobei die saure Quelle und die Stickstoff-Quelle in einer einzigen chemischen Verbindung vorliegen, die aus der Gruppe ausgewählt ist, bestehend aus Ammoniumphosphat, Ammoniumpolyphosphat, Ammoniumpyrophosphat und Mischungen derselben.
• (14) Flammenhemmende Polyolefin-Zusammensetzung, die Folgendes umfasst: (a) eine Polyolefinpolymer-Zusammensetzung; (b) eine Quelle für einen cyclischen Organophosphorsäurekatalysator, (c) eine Stickstoff-Quelle, ausgewählt aus der Gruppe bestehend aus Aminen, Harnstoffen, Guanidinen, Guanaminen, s-Triazinen, Aminosäuren, Salzen davon einschließlich Phosphat-, Phosphonat-, Phosphinat-, Borat-, Cyanurat- und Sulfatsalzen, sowie Mischungen des Obigen und (d) ein ionisches Montmorillonoid-Phyllosilicat in einer Menge von etwa 0,1 bis etwa 2 Gew.-%.
• (15) Aufschäumende Zusammensetzung gemäß (14), wobei die Quelle für einen cyclischen Organophosphorsäurekatalysator eine bicyclische Organophosphor-Verbindung ist und die Stickstoffquelle eine Komponente umfasst, die ausgewählt ist aus der Gruppe bestehend aus Melamin, Harnstoff, Benzoguanamin, Ammelin, Guanidin, Cyanoguanidin und Glycin; Melaminphosphat, Melaminpyrophosphat und Melaminpolyphosphat; Ammoniumphosphat, Ammoniumpyrophosphat und Ammoniumpolyphosphat, Ethylendiaminphosphat, Melamin- oder Ammoniumcyanurat, Melamin- oder Ammoniumborat und Mischungen davon.
• (16) Aufschäumende Zusammensetzung gemäß (15), wobei die bicyclische Organophosphor-Verbindung und die Stickstoffquelle in einer Menge von etwa 5 bis etwa 25 Gew.-% im Aggregat vorhanden sind.
• (17) Aufschäumende Zusammensetzung gemäß (16), weiterhin umfassend ein Zink- oder Mangansalz als Cosynergisten.
• (18) Aufschäumende Zusammensetzung gemäß (17), wobei die bicyclische Organophosphor-Verbindung und die Stickstoffquelle in einer Menge von weniger als etwa 18 Gew.-% im Aggregat vorhanden sind und die Zusammensetzung durch eine Flammbarkeitseinstufung von 94V-0 gekennzeichnet ist.
• (19) Aufschäumende Zusammensetzung gemäß (14), wobei die Quelle für die cyclische Organophosphor-Verbindung Pentaerythritphosphatalkohol umfasst.
• (20) Aufschäumende Zusammensetzung gemäß (14), wobei das Gewichtsverhältnis der Quelle für den cyclischen Organophosphorsäure-Katalysator zur Stickstoffquelle etwa 70:30 bis etwa 30:70 beträgt.
• (21) Aufschäumende Zusammensetzung gemäß (20), wobei das Gewichtsverhältnis der Quelle für den cyclischen Organophosphorsäure-Katalysator zur Stickstoffquelle etwa 60:40 bis etwa 40:60 beträgt.
• (22) Aufschäumende Zusammensetzung gemäß (21), wobei das Gewichtsverhältnis der Quelle für den cyclischen Organophosphorsäure-Katalysator zur Stickstoffquelle etwa 45:55 bis etwa 55:45 beträgt.
• (23) Aufschäumende Polypropylen-Zusammensetzung gemäß (14), wobei die Stickstoffquelle Melaminphosphat ist.
• (24) Aufschäumende Zusammensetzung gemäß (14), wobei die Zusammensetzung weiterhin ein Metalloxid oder ein Metallsalz umfasst.
• (25) Flammhemmende Additiv-Zusammensetzung zum Dispergieren in einer Matrixpolymer-Zusammensetzung zur Förderung des Aufschäumens, umfassend: (a) eine Säurekatalysatorquelle; (b) eine Stickstoffquelle; (c) ein ionisches Phyllosilicat mit einer Kationenaustausch-Kapazität von wenigstens etwa 5 Milliäquivalenten auf 100 g davon und (d) gegebenenfalls einschließlich eines organischen Polyols als carbonifizierendes, verkohlungsfördernden Mittels, wobei das ionische Schicht-Phyllosilicat in einer Menge von etwa 0,5 bis etwa 10 Gew.-% der Additivzusammensetzung vorhanden ist.
• (26) Flammhemmende Additiv-Zusammensetzung gemäß (25), wobei das ionische Schicht-Phyllosilicat ein ionisches Montmorillonoid-Phyllosilicat ist.
• (27) Flammhemmende Additiv-Zusammensetzung gemäß (26), wobei die Säurekatalysatorquelle eine Komponente umfasst, die aus der aus bicyclischen Organophosphorverbindungen und Ammoniumpolyphosphat bestehenden Gruppe ausgewählt ist.
• (28) Flammhemmende Additiv-Zusammensetzung gemäß (25), wobei die Stickstoffquelle eine Melaminverbindung ist.
• (29) Flammhemmende Additiv-Zusammensetzung gemäß (25), wobei die Säurekatalysatorquelle Pentaerythritphosphatalkohol umfasst.
• (30) Aufschäumende Zusammensetzung gemäß (25), wobei die Zusammensetzung weiterhin ein Metalloxid oder Metallsalz umfasst.

Thus, the present invention relates to:

• (1) An intumescent polymer composition comprising (a) a matrix polymer composition, (b) an acid catalyst source, (c) a nitrogen source, and (d) an ionic phyllosilicate in an amount of about 0.1 to about 2% by weight of the composition, wherein the ionic phyllosilicate has a cation exchange capacity of at least 5 milliequivalents per 100 g thereof and the ionic phyllosilicate can synergistically promote the foaming of the composition,
• (2) The foaming composition according to (1), wherein the ionic phyllosilicate is an ionic montmorillonoid phyllosilicate.
• (3) The foaming composition according to (2), wherein the montmorillonoid mineral comprises a clay selected from the group consisting of montmorillonite and hectorite.
• (4) The foaming composition according to (2), wherein the ionic montmorillonoid phyllosilicate is an organic montmorillonoid mineral.
• (5) The foaming composition according to (2), wherein the montmorillonoid mineral is a sodium montmorillonite.
• (6) The foaming composition according to (2), wherein the acid catalyst source is an organophosphorus compound.
• (7) The foaming composition according to (2), wherein the nitrogen source is melamine or a salt thereof.
• (8) The foaming composition according to (2), wherein the matrix polymer is a polyolefin and the ionic montmorillonoid phyllosilicate is present in an amount of about 0.3 to about 1.5% by weight of the composition.
• (9) The foaming composition according to (8), wherein the ionic montmorillonoid phyllosilicate is present in an amount of about 0.5 to about 0.7% by weight of the composition.
• (10) The foaming composition according to (8), wherein the matrix polymer composition consists essentially of polypropylene.
• (11) The foaming composition according to (1), wherein the composition further comprises a metal oxide or metal salt.
• (12) The foaming composition according to (11), wherein the composition comprises a metal salt and the salt is zinc borate.
• (13) The foaming composition according to (2), wherein the acid source and the nitrogen source are in a single chemical compound selected from the group consisting of ammonium phosphate, ammonium polyphosphate, ammonium pyrophosphate and mixtures thereof.
• (14) A flame-retardant polyolefin composition comprising: (a) a polyolefin polymer composition; (b) a source of a cyclic organophosphoric acid catalyst, (c) a nitrogen source selected from the group consisting of amines, ureas, guanidines, guanamines, s-triazines, amino acids, salts thereof, including phosphate, phosphonate, phosphinate, Borate, cyanurate and sulfate salts, and mixtures of the above, and (d) an ionic montmorillonoid phyllosilicate in an amount of from about 0.1 to about 2 percent by weight.
• (15) The foaming composition according to (14), wherein the source of a cyclic organophosphoric acid catalyst is a bicyclic organophosphorus compound and the nitrogen source comprises a component selected from the group consisting of melamine, urea, benzoguanamine, ammeline, guanidine, cyanoguanidine and glycine; Melamine phosphate, melamine pyrophosphate and melamine polyphosphate; Ammonium phosphate, ammonium pyrophosphate and ammonium polyphosphate, ethylenediamine phosphate, melamine or ammonium cyanurate, melamine or ammonium borate, and mixtures thereof.
• (16) The foaming composition according to (15), wherein the bicyclic organophosphorus compound and the nitrogen source are present in an amount of about 5 to about 25% by weight in the aggregate.
• (17) An intumescent composition according to (16), further comprising a zinc or manganese salt as a co-synergist.
• (18) The foaming composition according to (17), wherein the bicyclic organophosphorus compound and the nitrogen source are present in an amount of less than about 18% by weight in the aggregate, and the composition is characterized by a flammability rating of 94V-0.
• (19) An intumescent composition according to (14), wherein the source of the cyclic organophosphorus compound comprises pentaerythritol phosphate alcohol.
• (20) The foaming composition according to (14), wherein the weight ratio of the source of the cyclic organophosphoric acid catalyst to the nitrogen source is about 70:30 to about 30:70.
• (21) The foaming composition according to (20), wherein the weight ratio of the source of the cyclic organophosphoric acid catalyst to the nitrogen source is about 60:40 to about 40:60.
• (22) The foaming composition according to (21), wherein the weight ratio of the source of the cyclic organophosphoric acid catalyst to the nitrogen source is about 45:55 to about 55:45.
• (23) The foaming polypropylene composition according to (14), wherein the nitrogen source is melamine phosphate.
• (24) The foaming composition according to (14), wherein the composition further comprises a metal oxide or a metal salt.
• (25) A flame-retardant additive composition for dispersing in a foaming-promoting matrix polymer composition, comprising: (a) an acid catalyst source; (b) a nitrogen source; (c) an ionic phyllosilicate having a cation exchange capacity of at least about 5 milliequivalents per 100 grams thereof; and (d) optionally including an organic polyol as a carbonizing char promoter, wherein the ionic layer phyllosilicate is present in an amount of about 0.5 to about 10% by weight of the additive composition is present.
• (26) The flame retardant additive composition according to (25), wherein the ionic layer phyllosilicate is an ionic montmorillonoid phyllosilicate.
• (27) The flame-retardant additive composition according to (26), wherein the acid catalyst source comprises a component selected from the group consisting of bicyclic organophosphorus compounds and ammonium polyphosphate.
• (28) The flame retardant additive composition according to (25), wherein the nitrogen source is a melamine compound.
• (29) The flame-retardant additive composition according to (25), wherein the acid catalyst source comprises pentaerythritol phosphate alcohol.
• (30) The foaming composition according to (25), wherein the composition further comprises a metal oxide or metal salt.

Claims (19)

An intumescent polymer composition comprising (a) a matrix polymer composition, (b) an acid catalyst source, (c) a nitrogen source, and (d) an ionic phyllosilicate in an amount of 0.1-2% by weight of the A composition wherein the ionic phyllosilicate has a cation exchange capacity of at least 5 milliequivalents per 100 grams thereof and the ionic phyllosilicate can synergistically promote the foaming of the composition, with the proviso that the combination of acid catalyst source and nitrogen source does not Phosphoramide with a T _g of at least 0 ° C. foaming Composition according to claim 1, wherein the ionic phyllosilicate is a montmorillonite-type ionic Phyllosilicate is. foaming Composition according to claim 2, wherein the montmorillonite-type mineral comprises a clay, the selected from the group is composed of montmorillonite and hectorite. foaming Composition according to claim 2, wherein the montmorillonite-type ionic phyllosilicate is an organic Montmorillonite-type mineral is. foaming Composition according to claim 2, wherein the montmorillonite-type mineral is a sodium montmorillonite is. An intumescent composition according to claim 2, wherein the acidic catalyst source is an organ is nophosphorus compound. foaming Composition according to claim 2, wherein the nitrogen source is melamine or a salt thereof. foaming Composition according to claim 2, wherein the matrix polymer is a polyolefin and the montmorillonite-like ionic phyllosilicate is present in an amount of 0.3-1.5% by weight of the composition. foaming Composition according to claim 8, wherein the montmorillonite-type ionic phyllosilicate in a Amount of 0.5-0.7 Wt .-% of the composition is present. foaming Composition according to claim 8, wherein the matrix polymer composition consists essentially of Polypropylene exists. foaming Composition according to claim 1, wherein the composition further comprises a metal oxide or metal salt includes. foaming Composition according to claim 11, wherein the composition comprises a metal salt and the salt Zinc borate is. foaming Composition according to claim 2, wherein the acid source and the nitrogen source in a single chemical compound selected from the group consisting of ammonium phosphate, ammonium polyphosphate, ammonium pyrophosphate and mixtures thereof. A flame retardant additive composition for dispersing in a matrix polymer composition to promote foaming, comprising: (a) an acidic catalyst source, (b) a nitrogen source, (c) a cation exchange ionic phyllosilicate -Capacity of at least 5 milliequivalents per 100 grams thereof and (d) optionally including an organic polyol as a char formation promoter, wherein the layered ionic phyllosilicate is present in an amount of 0.5 to 10 weight percent of the additive Provided that the combination of acid catalyst source and nitrogen source is not phosphoramides having a T _g of at least 0 ° C. Flame retardant additive composition according to claim 14, wherein the layered ionic phyllosilicate is a montmorillonite-type ionic phyllosilicate. Flame retardant additive composition according to claim 15, wherein the acidic catalyst source comprises a component, selected from the group is composed of bicyclic organophosphorus compounds and Ammonium polyphosphate. Flame retardant additive composition according to claim 14, wherein the nitrogen source is a melamine compound. Flame retardant additive composition according to claim 14, wherein the acidic catalyst source is pentaerythritol phosphate-alcohol includes. Flame retardant additive composition according to claim 14, wherein the composition further comprises a metal oxide or metal salt includes.